Control of insects,acarinae and nematodes with basically substituted 1-cyano-o-carbamoyl-formoximes

ABSTRACT

NEW BASICALLY SUBSTITUTED 1-CYANO-O-CARBOMOYL-FORMOXIMES ARE DECRIBED AS INSECTICIDES, ACARCIDES AND NEMATOCIDES, WHICH ARE DISTINGUISHED FROM KNOW CARBANOYLOXIMES BY PRONOUCED SYSTEMIC INSECTICIDAL, ACARICIDAL AND NEUMATOCIDAL ACTION. A TYPICAL COMPOUND IS 1-DIETHYLAMINO-O-(N&#39;&#39;-METHYLCARBAMOYL) - FORMOXIME. PROCESS FOR THE PRODUCTION OF THESE COMPOUNDS ARE DESCRIBED AS WELL AS PESTICIDAL COMPOSITIONS CONTAINING THESE COMPOUNDS AS ACTIVE SUBSTANCES.

United States Patent Office Patented Apr. 9, 1974 CONTROL OF INSECTS,ACARINAE AND NEMA- TODES WITH BASICALLY SUBSTITUTED 1-CYANO-O-CARBAMOYL-FORMOXIMES Hans Ulrich Brechbuhler, Basel, and KurtGubler, Riehen, Switzerland, assignors to Geigy Chemical Corporation,Ardsley, N.Y.

No Drawing. Original application July 23, 1969, Ser. No. 844,163, nowPatent No. 3,673,236. Divided and this application Apr. 13, 1972, Ser.No. 243,851

Claims priority, application Switzerland, July 24, 1968,

11,105/ 68 Int. Cl. A01n 9/20 U.S. Cl. 424-304 11 Claims ABSTRACT OF THEDISCLOSURE New basically substituted l-cyano-O-carbamoyl-formoximes aredescribed as insecticides, acaricides and nematocides, which aredistinguished from known carbamoyloximes by pronounced systemicinsecticidal, acaricidal and nematocidal action. A typical compound isl-diethylamino-O-(N'-methylcarbamoyl) formoxime. Processes for theproduction of these compounds are described as well as pesticidalcompositions containing these compounds as active substances.

This is a division of application Ser. No. 844,163 filed July 23, 1969,HOW U.S. Pat. NO. 3,673,236.

Detailed Description The present invention concerns newcarbamoyl-formoximes, namely 1-cyano-O-carbamoyl-formoximes having abasic group in l-position, process for the production thereof,pesticidal agents containing these new compounds as active substance, aswell as methods for the control of pests using the new active substancesor agents containing them.

In the South African Pat. No. 66/6759, a number of carbamoyl-oximes ofaliphatic aldehydes have already been suggested as insecticidal,acaricidal and nematocidal active substances. In French Pat. No.1,498,899 l-cyanol-alkylthio-O-carbamoyl-formoximes, among others, aredescribed therein. This group of active substances, however does notpossess any or only insufficient systemic insecticidal properties.Individual members of this group are, moreover, phytotoxic and toxic forwarm-blooded animals.

The compounds of the present invention are basically substituted l-cyanoO carbamoyl formoximes of the Formula 1:

CN =NOCON wherein Examples of lower alkyl radicals represented by R to Rhaving 1 to 5 carbon atoms are methyl, ethyl, n-propyl, isopropyl,n-butyl, tert-butyl, isobutyl and pentyl radicals.

Examples of lower alkenyl radicals R are the allyl, methallyl orpropenyl radical. Cyeloalkyl radicals R are preferably monocyclicradicals such as cyclopropyl, l-methylcyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl. Substiuted alkyl radicals contain, forexample, the following substituents: hydroxy, halogen, lower alkoxy,alkylthio, alkylarnino, dialkylamino, whereby alkyl always representslower alkyl of from 1 to 5 carbon atoms.

A 5- or 6-membered heterocyclic radical formed by R and R and theadjacent nitrogen atom is preferably saturated and can contain otherhetero atoms such as another nitrogen atom or oxygen atom. Theseheterocyclic radicals can'also contain substituents such as lower alkyl,lower alkoxycarbonyl, etc. Preferred heterocyclic radicals are: thepiperidino, piperazino, 4-methylpiperazino, 4 alkoxycarbonyl piperazinoor the morpholino radical.

The novel 1-cyano-O-carbamoyl-formoximes of the Formula I are producedaccording to the invention by reacting a l-cyanoformoxime of the FormulaH:

R1 CN N(|3=NOH R2 either (a) with an isocyanate of the Formula III:

R NCO (III) or (b) with a carbamic acid halide of the Formula IV:

HaICN (I; R4 (IV) wherein Hal represents chlorine or bromine, or

(c) with the components forming the carbamic acid halide of Formula IV,namely with phosgene and an amine of the Formula V:

R4 (V preferably in the presence of an acid-binding agent and a solventor diluent which is inert towards the reaction components. In theFormulas II to V, the symbols R to R have the meanings given for FormulaI.

formoximes of Formula I in which R represents hydrogen, a mixture of anisocyanate of Formula III and an N-mono-alkyl-carbamic acid halide ofthe formula Hal-fiJ-NHR;

can also be used.

The reactions according to the invention are performed in the presenceof acid-binding agents such as inorganic bases, e.g. hydroxides, oxidesand carbonates of alkali and alkaline earth metals, and organic nitrogenbases, for example tertiary amines such as pyridine, triethylamine,triethylene-diamine, etc., as well as organotin compounds. The reactionsare carried out in the presence of solvents and diluents which are inerttowards the reaction components, e.g. in ethers and ether-type compoundssuch as diethylether, propyl ethers, dioxane; ketones such as acetone,methylethyl ketone; amides such as N,N-alkylated carboxylic acid amides;in halogenated hydrocarbons or aliphatic and aromatic hydrocarbons. Thenovel carbamoyl oximes are obtained according to the invention in goodto very good yields. They are soluble in the usual organic solvents andwater and are stable. Some of the starting materials of Formula II usedfor the reactions according to the invention are known. The compoundswhich have not previously been described can be obtained according tothe method described by W. 'Steinkopf et al., [.l.pr.Chemie (2), 83,453-470 (1911)], by reacting 1- chloro-l-cyano-formoxime with primaryand secondary amines.

It is known that oximes can exist in two stereoisomeric forms, thesynand the anti-form. The l-cyano-O-carbamoyl-formoximes of Formula Ican also exist in these two forms. For this reason the terml-cyano-O-carbamoylformoxirnes of Formula I" should be understood torepresent both of these stereoisomeric forms.

The following examples illustrate the process according to theinvention. The temperatures are given in degrees centigrade and allparts and percentages are by Weight unless otherwise specified.

EXAMPLE 1 (a) 200 ml. of a 33% solution of dimethyl amine in absoluteethanol are added .to 500 ml. of dioxane and then 24 g. ofl-chloro-l-cyano-formoxime in 100 ml. of absolute dioxane are addeddropwise with vigorous stirring under an atmosphere of nitrogen. Thetemperature rises to 40 and a precipitate of dimethylaminehydrochlorideis formed. Stirring is continued for 16 hours at room temperature andfinally for 2 hours at 60.

The solvents are removed by suction under vacuum, the residue isdissolved in a small volume of water, acidified (pH 3-4) with phosphoricacid and extracted with diethyl ether. The ethereal extracts are driedwith anhydrous sodium sulfate, and the ether is removed under vacuum. Inthis manner, 21.4 g. of l-dimethylamino-lcyano-formoxime are obtained asbrownish crystals having a melting point of 112.

(b) 5.3 g. of 1-dirnethylamino-I-cyano-formoxime are dissolved in 50 ml.of dioxane, treated with 0.25 ml. of triethyl amine, and 7.5 m1. ofmethylisocyanate are added thereto. This mixture is kept for 16 hours at-40-50. After cooling, the dioxane is removed under vacuum and theresidue is recrystallized from ethanol. In this manner, 69 g. of whitecrystals (M.P. 114-117") of l-dimethylamino- I-cyano O(N'-methylcarbamoyl)-formoxime are obtlalirzietliis'lzhe mother liquoryields a further 4.5 g., M.P.

EXAMPLE 2 42.8 g. of l-morpholino-l-cyano-formoxime [producedanalogously to Example 1(a)] and 33.2 g. of dimethylcarbamic acidchloride are dissolved in 700 ml. of dioxane, and then treated with 44.2g. of anhydrous potassium carbonate. The mixture is allowed to react for16 hours at 80 with vigorous stirring in an atmosphere of nitrogen.After cooling, the solid portion is removed by filtratron and thedioxane is removed by distillation in vacuum. The residue isrecrystallized from water. In this manner, 39.5 g. ofl-morpholino-l-cyano-O-(N'-dimethyl-carbamoyl)-formoxime, M.P. 120-121",are obtained.

EXAMPLE 3 9.6 g. of a 50% by weight suspension of sodium bydude inparaflin oil are diluted under nitrogen atmosphere with 100 m1. of drytetrahydrofuran. A solution of 31 g. of morpholino-l-cyano-formoxime in200 m1. of dry tetrahydrofuran is added dropwise at room temperaturewith stirring vigorously to this suspension. Stirring is continued at35-40 for 30 minutes. This mixture is then added in small portions at -5to a stirred solution of 39.6 g. of phosgene in 400 ml. of dry ether.Stirring is continued at room temperature for 30 minutes. The excess ofphosgene is then removed in vacuo. A solution of 22.5 g. ofdimethylamine in 100 ml. of dry tetrahydrofuran is then added dropwiseat room temperature and the whole is stirred for 16 hours at roomtemperature. The reaction mixture is then heated to 60 for one hour, thesolution is filtered after cooling and the solvent is removed in vacuo.

The residue is washed with hexane in order to remove the paraflin oiland then recrystallized from a water/ ethanol mixture. Thusl-morpholino-l-cyano-O- (N'-dimethyl-carbamoyl) -formoxime melting at120-121 is obtained.

The following compounds of Formula I were produced analogously to theprocesses described in the Examples:

Melting point, Compounds degrees l-methylarnino-l-e'ano-O-(N-methylearbamoyl)- 58-59l-ethylamino-l-cyano-O-(N-methylearbamoyD-formoxime. 132-1421-diethy1amino-1-cayno-O-(N-methylcarbamoyl) iormoxii'nenui 60-91 l-nr0armno yan foiim x imefiu 112-114 l-isopropylamin yano ethylearbamoyD-forrnoxime 131-136 l-n-butylamino-l-cyano-(N'-methylcarbarnoyl)-formoxime. 101-102 l-isobutylamino-l'cyano-(N-methylcarbamoyl)-iormoxime 133-134 1-tert-butylamino-1-cyano-O-(N-methylcarbamoyl)-formoxime 109-112 1-cyclopropylanflno-l-cyano-O -(N-methylcarbam0yl)-formoxime 139 l-piperidino-l-eyano-O-(N'-rnethylearbamoyl) -forrnoxime154 l-morpholino-Lcyano-O-(N-methylcarbamoyl)-t'ormoxi1ne 120-168l-morpholino-l-cyano-O -(N'dimethylcarbamoyl)- formoxime 120-121l-diethylamino-l-cyano-O-(N-dimethylcarbamoyl)- forrnoxime O111-di-n-propylarnino-1-cyano-O-(N-methylearbamoyl)- formoxime 01]l-anilino-l-cyano-O-(N-methylcarbamoyl)-iormoxime 172-174l-piperidino-l-eyano-0-(N-methylcarbamoyl)-forznoxime 154l-piperazino-l-cyano-O-(N-rnethylcarbamoyl)dormoxime. 2021-(4-methyl-piperazino) -1-cyano-O-(N-methylcarbamoyl)- formoxime 821-(4-ethoxycarbonyl-piperazino) -1-cyano-(N '-methylcarbamoyl)-lorrnoxime T 105 1-(4-ethoxycarbonyl-piperazino) -1-cyano-O-(N-d1methylearbamoyD-formoxime 1371-dimethylamino-1-cyano-O-(N-ethylcarbamoyl)- formoxime 811-dimethy1amino-l-cyano0-(N-isopropylcarbamoyl)- forrnoxime 99l-dimethylarnino-l-eyano-O-(N-allylcarbamoyl-) fonnoxime 86l-dimethylarnino-l-cyano-O-(N -n-propylca-rbamoyl)- formoxime 74l-morpholino-l-eyano-O-(N'-ethylcarbamoyl) -f0rmox1me Pastel-diethylarnino-l-cyano-O-(N-ethylcarbamoyl)dormoxirne. O11l-tetrahydroturiurylamino-O-(Nmethylcarbamoyl)- formoxime 121-122 Theproduction of pesticidal agents according to the invention is performedin a known manner by intimate mixing and grinding of active substancesof the general Formula I together with suitable carriers, optionallywith the addition of dispersing agents, absorbents, or solvents, whichare inert towards the active substances. The novel active substances canbe prepared in the following forms:

solid preparations: dusts, scattering agents, granulates,

(coated granulates, impregnated granulates and homogeneous granulates);water-dispersible concentrates of the active substance:

wettable powders, pastes, emulsions; liquid preparations: solutions,aerosols.

The concentration of active substance in these preparations is from 0.01to Other biocidally active substances or agents can be admixed with theagents described according to the invention. Thus, in addition to thesaid active substances of the general Formula I, the new agents maycontain, for example, other insecticides, fungicides, bactericides,fungistatic and bacteriostatic substance or other nematocides in orderto broaden the range of action. The agents according to the inventionmay also contain plant fertilizers, trace elements, etc.

The novel active substances are used for soil disinfection in the formof solid or liquid agents. For soil disinfection, those agents whichassure an even distribution of the active substance throughout a layerof soil 15 to 25 cm. deep are especially favorable. The method and formof application are, in particular, dependent upon the type of soil peststo be controlled, the climate and the nature of the soil.

Since the novel active substances are not phytotoxic acid do notadversely affect seed germination they can be used before seedingwithout observing a waiting time and in crops which have already beenplanted.

The following forms for application of the pesticides according to theinvention serve to illustrate the invention; where not expressly statedotherwise, parts and percentages are by weight.

Dust

The following ingredients are used to produce (a) a and (b) a2% dust:

(a) 10 parts of l-n-butylamino-l-cyano-O-(N-methylcarbamoyl) -formoxime,

5 parts of highly dispersed silicic acid,

85 parts of talcum;

(b) 2 parts of l-morpholino-l-cyano-O-(N-dimethylcarbarnoyl)-formoxime,

1 part of highly dispersed silicic acid,

97 parts of talcum.

The active substances are mixed and ground with the carriers. The dustsobtained are used, e.g., for the control of cockroaches and ants, etc.in buildings, and also for plant protection.

Granulate The following ingredients are used to produce a 5% granulate:

5 parts of isopropylamino-l-cyano-O-(N'-methylcarbamoyl) -formoxime,

0.25 part of epichlorohydrin,

0.25 part of octaethyleneglycol ether,

3.50 parts of polyethyleneglycol of a molecular weight of about 400,

91 parts of kaolin (particle size 0.3-0.8 mm.).

The active ingredient is mixed with epichlorohydrin and then dissolvedin 6 parts of acetone, and the polyethyleneglycol and octaethyleneglycolether are added thereto. The solution obtained is sprayed onto kaolinand then the acetone is evaporated in vacuo. The granulate obtained issuitable for the protection of plants and stored goods.

Wettable powder For the production of a 50% [(a) and (b)], a 25% [(c)],and a 10% [(d)] wettable powder, the following components are used:

(a) 50 parts ofl-dimethylamino-l-cyano-O-(N'-methylcarbamoyl)-formoxime,

5 parts of naphthalene sulfonic acid/ benzene sulfonic acid/formaldehyde condensation product,

5 parts of nonylphenyl sulfonate,

5 parts of champagne chalk,

20 parts of silicic acid,

parts of kaolin;

(b) 50 parts of l-diethylamino-l-cyano-O-(N-dimethylcarbamoyl)-formoxime,

5 parts of nonylphenyl sulfonate,

10 parts of calcium lignin sulfonate,

1 part of champagne chalk/hydroxyethyl cellulose mixture parts ofsilicic acid,

14 parts of kaolin;

(c) parts of l-n-propylamino-1-cyano-'O-(N'-methylcarbamoyl -formoxime,

5 parts of sodium oleyl methyl tauride,

2.5 parts of naphthalene sulfonic acid/formaldehyde condensationproduct,

0.5 part of carboxymethyl cellulose,

5 parts of neutral potassium-aluminum silicate,

62 parts of kaolin;

6 (d) 10 parts of l-n-butylamino-l-cyano-O-(N'-methyl carb amoyl)-formoxime, 3 parts of a mixture of the sodium salts of saturated fattyalcohol sulfates, 5 parts of naphthalene sulfonic acid/formldehydecondensation product, 82 parts of kaolin.

The active ingredients are intimately mixed with the additives insuitable mixers and ground in mills and rollers. Wettable powders areobtained which can be diluted with water to form suspensions of anydesired concentration. Such suspensions are used primarily in plantprotection for the control of biting and sucking insects.

Paste The following ingredients are used to produce a 45% paste:

45 parts of l-diethylamino-l-cyano-O-(N'-methy1carbamoyl) -formoxime,

5 parts of sodium aluminium silicate 15 parts of cetyl octaethyleneglycol ether 2 parts of spindle oil,

10 parts of polyethyleneglycol of a molecular weight of about 400,

23 parts of water.

The active ingredient is intimately mixed and ground with the additivesin apparatus suitable therefor. A paste is obtained from which, bydilution with water, suspensions of any concentration desired can beproduced. These suspensions are suitable for the control of insects inplant protection.

Emulsion To produce a 10% emulsion concentrate,

10 parts of l-morpholino-l-cyano-O-(N-methylcarbamoyl) -formoxime,

55 parts of xylene,

32 parts of dimethyl formamide and 3 parts of an emulsifying agentconsisting of nonylphenyl decaethyleneglycol and calciumnonylphenylsulfonate (weight ratio about 1:1)

are mixed together. This concentrate can be diluted with water to formemulsions having concentrations suitable for the protection of plantsand stored goods.

Spray (a) 1 part ofl-methylamino-l-cyano-O-(N'-methylcarbamoyl)-formoxime are dissolved in99 parts of water;

(b) 2 parts of 1-dimethylamino-l-cyano-O-(N'-methylcarbamoyD-formoximeare dissolved in 10 parts of xylene and 88 parts of petroleum;

(c) 2 parts of l-diethylaniino-l-cyano-o-(N'-methylcarbamoyl)-formoximeand 3 parts of dichlorophenyltrichloroethane are dissolved in parts ofkerosene.

These solutions are sprayed with pressure Sprayers. The Solution (a) isadvantageously used for the control of leaf aphids on fruit trees andother plants. The Solutions (b) and (c) are used in particular for thecontrol of flies and mosquitoes in buildings, storerooms and slaughterhouses.

Insecticidal and acaricidal tests with the compounds of Formula I haveshown that the novel l-cyano-O-carbamoyl-formoximes have a very goodsystemic insecticidal action; in addition, they are good to very goodstomach and contact poisons. Tests of their action were made withinsects of the families Muscidae, Stomoxidae and Culicidae, e.g. withpolyvalent resistant and normally sensitive house flies (Muscadomestica), stable flies (Stomoxys calcitrans) and mosquitoes (e.g.,Aedes aegypti, Culex fatigans, Anopheles stephensi); with insects of thefamilies Curculionidae, Bruchididae, Dermestidae, Tenebrionidae andChrysomelidae, e.g. granary weevils (Sitophilus granarius), bean beetles(Bruchidus obtectus), larder beetles (Dermestes vulpinus), yellow mealworms (Tenebrio molitor), Colorado potato beetles (Leptinotarsadecemlineata) and their stages of development; with insects of thefamily Pyralididae, e.g. Mediterranean flour moths (Ephestiakqihniella), as well as of the family Blattidae, e.g. cockroaches(Phyllodromia germam'ca, Periplaneta americana, Blatta orientalis), thefamily Aphididae, e.g. bean aphids (Aphis fabae); in addition, withinsects of the family Pseudococcidae, e.g. citrus mealybu-gs(Planocaccus citri) and of the family Locustidae, such as migra torylocusts (Locusta migratoria). The tests on the said bean aphids, citrusmealybugs and migratory locusts demonstrate a systemic action.

In addition, the active substances of the Formula I according to theinvention have a good action on the larval and adult stages of spiders,eg of the families Acarinae, Ixodidae, Arachnidae and Argasidae.

Furthermore the active substances of Formula I have excellentnematocidal and soil-fungicidal properties.

In admixture with synergists such as succinic acid dibutyl ester,piperonyl butoxide, and auxiliaries having a similar action such asolive oil, peanut oil, etc., the range of action of the activesubstances according to the invention is broadened and, in particular,the insecticidal and acaricidal action is improved. In the same way, theinsecticidal action can be substantially broaded and adapted to theprevailing circumstances by the addition of other insecticides such asphosphoric, thiophosphoric and dithiophosphoric acid esters and amides,carbamic acid esters, halogenated hydrocarbons and analogues of DDTactive substance, as well as pyrethrins and synergists thereof.

Systemic insecticidal action In order to determine the systemic actionof the new compounds, cabbage, tomato and horesbean plants in flowerpots containing 600 cc. of humus are watered with 50 ml. of an aqueousemulsion containing 0.48% of active substance (prepared from a emulsionconcentrate).

After 24 hours the parts of the plants above ground are infested withthe test animals. 10 deserts locusts (Locusta nigratoria, 3rd stage) areplaced on each cabbage plant, 10 citrus mealybugs (Pseudococcus citri)on each tomato plant, and 10 bean aphids (Aphis fabae) on each horsebeanplant. All tests are duplicated. The time elapsing until all insects arein dorsal position is determined. (Test period 3 days, ambienttemperature 25-30).

(a) Tests with Locusia migratcria (8rd stage) (c) Tests with Aphis fabael-methylthio-l-cyanoO-(N-methylcarbamoyl)-formoxime (known from SouthAfrican Pat. No. 66/6,?59 or the French Pat. No. 1,498,899)

Stomach poison test In order to determine the action of the newcompounds as stomach poison, cabbage and potato plants in flower potsare sprayed until completely wet with an aqueous emulsion containing0.05% of active substance (prepared from a 10% emulsion concentrate).For a first test a third of the treated plants are used. After 1 hour 10Colorado beetle larvae (Leptinotarsa decemlineata, 3rd stage) are placedon each potato plant, and 5 desert locusts (Locusta migratoria, 3rdstage) are placed on each cabbage plant. The test is repeated with thesecond and third portions of the treated plants after 3 and 8 days,respectively. All tests are duplicated. The time elapsing until allinsects are in dorsal position is determined. (Test period 2 days,ambient temperature 25-30.)

Tests w ith Locusts migmtorz'a (3rd stage) Time elapsed (in hours) untilin dorsal position, when plants ave been infected by insects after-Active substance 1 hr. 8 days 8 daysl-diethylamino-l-cyano-O-(N'-methylcarbamoyl)-iormoxime 48 84l-morpholino-l-cyano-O-(N'-methylcarbamoyD-iormoxime 24 24 24l-piperidinc-l-cyano-0-(N-methylcarbamoyl)-iormoxime 24 48 48l-methylthio-l-cyano-O-(N-methylcarbamoyD-torrnoxime (known from SouthAfrican Pat. No. 66/6,759 or the French Pat. No. 1,498,899)

1 N 0 effect.

Contact poison test (a) Tests with cotton stainers (Dysdercusfascr'atus).- In order to determine the action as contact poison of thenew compounds, cotton plants in flower pots are sprayed until completelywet with an aqueous emulsion containing 0.025% of active substance(prepared from a 10% emulsion concentrate). After 1 hour, the plants areinfested with 10 adult cotton stainers each. All tests are duplicated.The time elapsing until all insects are in dorsal position isdetermined. (Test period 2 days, ambient temperature 25-30) TimeEffective concentration (inelfiegiusfg in d1percentI :oanato see n s ane on until 100% the g p in dorsal Active substance position 5 Activesubstance 1st day 8th day 1-d1ethy1am1no-1-cyan0-0-(N-methylcarbamoyl)-l-dimethylamino-l-cyano-o-(N-methylcarbamfor-momma 24 oyl) formox1me0.005 0.0025 1-d1-n-propylam1no-1-cyano-O-(N-methylcarbamoyl)-l-dlethylamino-l Iormomme" 24 oy1)-t'om1oxime. 0. 001 0. 001l-tert-butylamrno-l-cyano-O-(N -methylcarbamoy1)-l-morpholino-l-cyano-O-(N-methylcarbamoyl)- o o q' I 24 1o formoxime0.005 4 0. 005 p qy y y 24 l-piperidino-l-cyano-O-(N-methylcarbamoyl)-l-methylthro-l-cyano-O-(N-1nethylcarbamoyl)-f0m10x1me fonnoxhne 0. 0010. 001

(known from South African Pat. No. 66/6,?59 or the Frenchl-tert-butylamino-l cyano-o-(N'-methylcaf- Pat. No. 1,498,899)bamoyD-formoxime 0. 001 0. 001

l-tetrahydrofurinrylamino-1-cyano-0-(N- 1 No efiect.methylcarbamoyD-formoxime 0. 005 0. 005l-tgrolohesyflamino-l-cyano-O-(N-methy1car- 0 005 0 005 amoy ormoxrme(b) Tests with citrus mealybugs (Pseudococcus cztrz). LpipmdinwlWane)(N, methylcarbamoyl) Tomato plants infested with citrus mealybugs aresprayed formoxime 0.001 0.001

l-methylthio-l-cyano-O-(N-methylcarbamoy1)- until completely wet with anaqueous emulsion containing fonnoxime (known from south Amcan Pat 0.025%of active substance (prepared from a 10% emul- No. 66/6,759 or theFrench Pat. No. 1,498,899) 0.02 0.02

sion concentrate). All tests are duplicated. The time elapsing until allinsects are in dorsal position is determined. (Test period 2 days,ambient temperature 25-30.)

Acaricidal action on Tetranychus urticae.-In order to determine theacaricidal properties of the new compounds, a test is carried out withbean leaves infested with adults, quiescent stages and eggs of the redspider mite (Tetranychus urticae). The bean leaves are treated untilcompletely wet with aqueous emulsions in concentrations of 0.1 and 0.05%of active substance (prepared from a 25% emulsion concentrate). Theconcentrations of active substance used which lead to 100% mortalityafter 6 days are determined.

Red spider mites which are resistant to phosphoric acid esters are usedas test animals. The test results are given in the following table.

1 No effect at 0.1.

Nematocidal action on Meloidogyne arenaria.-The amount of activesubstance calculated to give concentrations for application of 0.02,0.01, 0.005 and 0.0025% is thoroughly mixed with sand and subsequentlymixed with humus, infested with Meloidogyne arenaria. Tomato seedlingsare immediately planted in the fresh humus prepared as described above.Part of the prepared humus is stored for 8 days, and then used forplanting more tomato seedlings. After a test period of 28 days thenumber of root knots is determined. The minimum concentration of activesubstance preventing the formation of root knots is given in the table.

LDso p-o ratin Active substance mg./kg.

l-methylamino-l-cyano-O-(N-methylcarbamoyl)- fm'mmrime 2981-dimethylamino-1-cyano-0-(N-methylcarbamoyl)- fnrmmrirne 111l-di-n-propylamino-l-cyano-O-(N-methylcarbamoyl)- fm-mnrime 111l-n-butylamino-l-cyano-O-(N-methylcarbamoy1)- fnrmnxime 5351-tetrahydroiurfurylamino-l-cyano-O-(N-methylcarbamoyD-fnrmnxime 3751-methy1thio-1-cyano-0-(N'-methy1carbamoyl)-formoxime (known from theSouth African Pat. No. 66/6,?59 or the French Pat. No. 1,498,899) 52 Weclaim:

1. A method for combatting pests selected from the group consisting ofinsects, acarinae and nematodes, which method comprises contacting saidpests with a pesticidally effective amount of a compound of the formulawherein R represents hydrogen, or an unsubstituted or substituted loweralkyl radical with 1 to 5 carbon atoms in which said substituents arehydroxy, halogen, alkoxy, alkylthio, alkylamino or dialkylamino, whereinthe alkyl moiety has from 1 to 5 carbon atoms; R represents a loweralkyl radical with 1 to 5 carbon atoms, or a cycloalkyl radical with 3to 6 carbon atoms; R represents hydrogen or a lower alkyl radical with 1to 5 carbon atoms; and R represents a lower alkyl radical with 1 to 5carbon atoms or a lower alkenyl radical with 2 to 4 carbon atoms.

2. A method according to claim 1 in which the compound isl-diethylamino-1-cyano-O-N'-methyl-carbamoy1- formoxime.

3. A method according to claim 1 in which the compound isl-isopropylamino-1-cyan0-ON'-methyl-carbamoyl-formoxime.

4. A method according to claim 1 in which the compound isl-n-propylamino-1-cyano-O-N-methy1-carbamoyl-formoxime.

5. A method according to claim 1 in which the compound isl-n-butylamino-1-cyano-0-N'-mcthyl-carbamoyl-formoxime.

6. A method according to claim 1 in which the compound is1-methy1amino-1-cyano-O-N'-methyl-carbamoylformoxime.

7. A method according to claim 1 in which the compound is1-dimethylamino-1-cyano-O-N'-methyl-carbamoyl-formoxime.

8. A method according to claim 1 in which the compound isl-dimethylamino-1-cyano-O-N'-dimethyl-carbamoyl-formoxime.

9. A method according to claim 1 in which the compound isl-ethylamino-1-cyano-O-N-methylcarbamoylformoxime.

10. A method according to claim 1 in which the compound isl-isobutylamino-1-cyano-O-N-methylcarbamoylformoxime.

11. A composition for combatting pests selected from the groupconsisting of insects, acarina and nematodes, said compositioncomprising (1) as active ingredient a pesticidally effective amount of acompound of the formula wherein R represents hydrogen, or anunsubstituted or substituted lower alkyl radical with 1 to 5 carbonatoms in which said substituents are hydroxy, halogen, al-koxy,alkylthio, alkylamino or dialkylamino, wherein the alkyl moiety has from1 to 5 carbon atoms; R represents a lower alkyl radical with 1 to 5carbon atoms, or a cycloalkyl radical with 3 to 6 carbon atoms; Rrepresents hydrogen or a lower alkyl radical with 1 to 5 carbon atoms;and R represents a lower alkyl radical with 1 to 5 carbon atoms, or alower alkenyl radical with 2 to 4 carbon atoms, and (2) a suitablecarrier.

References Cited UNITED STATES PATENTS 9/1969 Payne vet al. 260-46146/1972 Brechbuhler et al. 260-4614 FOREIGN PATENTS 1,498,899 11/ 1966France.

US. Cl. X.R.

